EP0507404A2 - Detergent containing article - Google Patents
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- Publication number
- EP0507404A2 EP0507404A2 EP19920200913 EP92200913A EP0507404A2 EP 0507404 A2 EP0507404 A2 EP 0507404A2 EP 19920200913 EP19920200913 EP 19920200913 EP 92200913 A EP92200913 A EP 92200913A EP 0507404 A2 EP0507404 A2 EP 0507404A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- detergent
- sachet
- briquettes
- grams
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003599 detergent Substances 0.000 title claims abstract description 72
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000013042 solid detergent Substances 0.000 claims abstract description 13
- 239000004484 Briquette Substances 0.000 claims abstract description 12
- 238000004851 dishwashing Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- 239000003607 modifier Substances 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- -1 alkali metal behenate Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 230000006835 compression Effects 0.000 claims description 4
- 229940116224 behenate Drugs 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010790 dilution Methods 0.000 abstract description 2
- 239000012895 dilution Substances 0.000 abstract description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 8
- 229940078456 calcium stearate Drugs 0.000 description 7
- 239000008116 calcium stearate Substances 0.000 description 7
- 235000013539 calcium stearate Nutrition 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 235000019832 sodium triphosphate Nutrition 0.000 description 6
- 239000007844 bleaching agent Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 235000019359 magnesium stearate Nutrition 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 229920002257 Plurafac® Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002195 soluble material Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229920013807 TRITON DF-12 Polymers 0.000 description 2
- 229940061587 calcium behenate Drugs 0.000 description 2
- SMBKCSPGKDEPFO-UHFFFAOYSA-L calcium;docosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCC([O-])=O SMBKCSPGKDEPFO-UHFFFAOYSA-L 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- CFPOJWPDQWJEMO-UHFFFAOYSA-N 2-(1,2-dicarboxyethoxy)butanedioic acid Chemical class OC(=O)CC(C(O)=O)OC(C(O)=O)CC(O)=O CFPOJWPDQWJEMO-UHFFFAOYSA-N 0.000 description 1
- JBNHKYQZNSPSOR-UHFFFAOYSA-N 4-(carboxymethylperoxy)-4-oxobutanoic acid Chemical class OC(=O)CCC(=O)OOCC(O)=O JBNHKYQZNSPSOR-UHFFFAOYSA-N 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical class OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical class OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001860 citric acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical class OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940070721 polyacrylate Drugs 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- PYILKOIEIHHYGD-UHFFFAOYSA-M sodium;1,5-dichloro-4,6-dioxo-1,3,5-triazin-2-olate;dihydrate Chemical compound O.O.[Na+].[O-]C1=NC(=O)N(Cl)C(=O)N1Cl PYILKOIEIHHYGD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
- C11D17/044—Solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
Definitions
- the present invention relates to a sachet containing a detergent composition which is adapted for the delivery of detergent material into the wash liquor of an automatic washing machine.
- the invention is particularly useful in industrial ware washing machines.
- Sachets which contain detergent powder and which can deliver detergent ingredients in washing machines in a sequential manner, have been disclosed in the prior art.
- EP 132 726 (Henkel) relates to a sachet within a sachet, whereby the inner sachet consists of material which is water-soluble at a predetermined temperature, and whereby the outer sachet also contains a cleaning composition.
- US 4 155 292 (Procter) relates to a sachet within a sachet for machine dishwashing, whereby the inner watersoluble bag is filled with enzyme material, and the outer water-soluble sachet is filled with detergent material. It is, further, disclosed by this document that the release and the stability of the enzyme are controlled.
- EP 236 136A discloses a sachet of water permeable material comprising at least 2 compartments of which the first compartment is capable of releasing its contents, within 3 minutes and the second compartment is designed such that release of its contents is delayed for at least 5 minutes from the start of the wash process. From the examples it is clear that this sachet is only suitable for one single washing cycle.
- this constant level of detergent product is maintained during at least 15 consecutive washing cycles. It is another object of the invention that this detergent containing sachet can be simply prepared.
- briquettes are defined as solid detergent blocks which include several discretely shaped detergent particles such as tablets, cubes, etc.
- the present invention provides a sachet containing a detergent composition and adapted for use in association with a dishwashing machine wherein the detergent comprises 20-350 grams of detergent powder and one or more solid detergent briquettes, the weight of each briquette being in the range of 1-1OO grams and the total weight of the briquettes being 10-200 grams.
- a second aspect of the present invention concerns a process for the preparation of this sachet wherein the solid detergent briquettes are produced by compression and, thereafter, the sachet is filled with these detergent briquettes and with detergent powder.
- a third aspect of the invention relates to the use of the sachet in an industrial ware washing machine.
- the sachet of the invention is designed to deliver its contents in distinctly different ways: the detergent powder is released very rapidly to obtain the required detergent concentration in the first wash whereas the release of the material of the solid briquettes is delayed and/or retarded such that the drop in detergent concentration caused by the dilution effect of rinse water applied between consecutive washes is compensated for.
- the material of which the sachet is made may be water permeable, water dispersable or water soluble material.
- sachets made of water soluble material, such as polyvinyl alcohol, polyethylene oxide and methyl cellulose.
- polyvinyl alcohol (PVA) is preferably used as water soluble material.
- PVA-film is used containing in addition to PVA starch, plasticiser and water, such as the PVA-film coded LXP 910 1.5 mil supplied by Chris Craft Monosol USA.
- Both briquettes and powder generally contain detergent components usually found in detergent material suitable for use in industrial ware washing machines. These detergent components comprise a builder, an alkaline agent, a bleaching agent and one or more types of nonionic surfactant material.
- Alkaline agents which can be suitably used as constituents in the detergent composition of the invention are sodium- or potassium-hydroxide, -metasilicate and -carbonate.
- Preferred alkaline agents are sodium-metasilicate and -carbonate.
- the total level of alkaline agents is in the range of from 10% to 80% by weight, preferably from 30% to 70% by weight of the detergent composition.
- the detergent composition of the invention contains at least one type of builder material capable of reducing the level of free calcium ions in the wash liquor and preferably providing the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the substrate to be cleaned.
- the total level of the detergency builder may be from 10% to 70% by weight, preferably from 30% to 60% by weight of the detergent composition.
- Preferred builders are phosphate builders such as pyrophosphate, orthophosphate or tripolyphosphate and ion exchange builders such as crystalline (zeolite) or amorphous aluminosilicates.
- organic and inorganic polymers may be present; for example, polycarboxylate polymers, such as acrylic-maleic copolymers such as SOKALAN-types of polymers and acrylic acid polymers such as Norasol LMW 45 ND (ex NorsoHaas) or Goodrite K7058 D (ex BF Goodrich) may be present.
- organic detergency builders which may be effectively used in the detergent composition of the present invention are citrates, nitrilotriacetates, phytates, polyphosphonates, oxydisuccinates, oxydiacetates, carboxymethyloxy succinates, tetracarboxylates and oxidised heteropolymeric polysaccharides.
- Other preferred builder systems are precipitant builders such as those containing calcite and carbonate as described in EP-A-267 042.
- the detergent composition of the invention may, further, contain 1-5% by weight of an active chlorine bleach such as sodium dichloro-isocyanurate, or, alternatively, 5-20% by weight of an oxygen bleach such as a peroxy acid compound.
- an active chlorine bleach component is applied.
- an anti-foam agent such as a low-foaming nonionic surfactant in the wash liquor and such agents may indeed be incorporated in the detergent composition of the invention. Amounts of 0-5% by weight proved to be suitable.
- the detergent composition of the invention may further comprise suitable minor ingredients, such as bleach stabilizers, enzymes, etc.
- suitable minor ingredients such as bleach stabilizers, enzymes, etc.
- Additional components particularly suitable for the briquettes may be compaction aids, for instance calcium stearate, hydrophobic silica or talc powder.
- the amount of detergent powder in a sachet according to the present invention is in the range 25-200 grams.
- 30-80 grams of detergent powder is applied.
- the total weight of the detergent briquettes in such a sachet is also usually in the range 25-200 grams.
- 30-95 grams of detergent briquettes is applied. So, the weight of the total detergent composition in the sachet is, preferably, in the range 60-175 grams.
- the weight of each solid detergent briquette is preferred to be in the range 4-10 grams.
- the best results with regard to constantness of product delivery are obtained if a solubility modifier is incorporated in the solid detergent briquettes.
- the effect of this solubility modifier is that the delivery of the solid detergent briquettes into the wash liquor is retarded.
- the solubility modifier is preferably selected from the group consisting of metal salts of fatty acids containing 12-24 C-atoms, more preferably 18-22 C-atoms. More preferably, the solubility modifier is selected from earth alkali metal stearates and behenates, such as magnesium stearate, calcium stearate or calcium behenate. The most effective solubility modifier appeared to be a combination of an earth alkali metal stearate and an earth alkali metal behenate.
- the solid detergent briquettes may be prepared by compression or by hydration followed by solidification. They are preferably prepared by compression of detergent powder, in a BEPEX briquetting machine using a pressure ranging from 50 to 200 kN.
- the sachet according to the present invention is particularly suitable to be applied in an industrial single tank reuse ware washing machine. It was found that when using this sachet the product concentration in the wash liquor can be kept more or less constant during at least 15 consecutive washing cycles.
- the sachet When used in a washing machine, the sachet is preferably placed in the dispenser according to the British application 91 07083.9.
- This dispenser has a distinctive size and shape and is equipped with a sink reservoir and view holes so that it can be refilled in time with a new sachet according to the present invention.
- Another type of dispensing device which can be effectively used is a floating ring with a nett or grid onto which the sachet is placed.
- This type of dispenser is particularly effective in washing machines which do not have a protective bottom plate between the wash compartment and the wash tank. By using these dispensers, no dosing equipment is required, optimal use of the detergent material can be achieved and the risk of skin contact when handling the product is minimised.
- a detergent powder and 2 types of detergent briquettes were prepared, having the following compositions: powder (wt%) briquette I (wt%) briquette II (wt%) STP 53.0 53.0 53.0 Soda 17.8 15.8 15.8 SMS Oaq 25.0 25.0 25.0 Plurafac LF 403 1.7 1.7 1.7 Na.DCCA.2H2O 2.5 2.5 2.5 2.5 Magnesium stearate - 2.0 - Calcium stearate - - 4.0 100.0 ⁇ 100.0 ⁇ 100.0 ⁇
- magnesium stearate is incorporated as solubility modifier
- calcium stearate is the solubility modifier in briquette II.
- the water-soluble sachets were applied in a single tank reuse automatic ware washing machine (Electrolux type D 48-740) and the delivery profiles were obtained by sampling the wash liquor and subsequently carrying out alkalinity titrations of these samples. For the washing cycles 15°GH water was used.
- solubility modifier i.e. calcium stearate
- a detergent powder and detergent briquettes were prepared having the following compositions: Briquettes (%wt) Powder (%wt) STP 51.4 51.9 Soda 16.3 16.4 SMS Oaq 24.3 24 Plurafac LF 403 1.6 1.7 NaDCCA.2H20 3.4 3.4 Mg stearate 2.0 - Ca behenate 1.0 - Calcium chloride 2 aq - 2.1 100.0 ⁇ 100.0 ⁇
- a water soluble sachet consisting of PVA material was filled with 86 gram of these briquettes and 73 gram of this detergent powder.
- the sachet was applied in a single tank reuse automatic ware washing machine (Electrolux type D48-740) and the delivery profile was obtained by applying the method of example 1. In figure 3 this profile is shown. It can be seen that a reasonably constant concentration of the detergent product in the wash liquor was obtained during more than 10 washes.
- the LXP 910 1.5 mil film was found to be the most suitable PVA-containing material for the sachet of the present invention.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Detergent Compositions (AREA)
Abstract
Description
- The present invention relates to a sachet containing a detergent composition which is adapted for the delivery of detergent material into the wash liquor of an automatic washing machine. The invention is particularly useful in industrial ware washing machines.
- Sachets which contain detergent powder and which can deliver detergent ingredients in washing machines in a sequential manner, have been disclosed in the prior art.
- EP 132 726 (Henkel) relates to a sachet within a sachet, whereby the inner sachet consists of material which is water-soluble at a predetermined temperature, and whereby the outer sachet also contains a cleaning composition. US 4 155 292 (Procter) relates to a sachet within a sachet for machine dishwashing, whereby the inner watersoluble bag is filled with enzyme material, and the outer water-soluble sachet is filled with detergent material. It is, further, disclosed by this document that the release and the stability of the enzyme are controlled.
- EP 236 136A (Unilever) discloses a sachet of water permeable material comprising at least 2 compartments of which the first compartment is capable of releasing its contents, within 3 minutes and the second compartment is designed such that release of its contents is delayed for at least 5 minutes from the start of the wash process. From the examples it is clear that this sachet is only suitable for one single washing cycle.
- Solid detergent briquettes containing components which raise the solubility have also been disclosed in the prior art, for instance in EP 203 523 A (Henkel).
- It is an object of the present invention to provide a sachet containing a detergent composition which sachet is designed such that when used in a washing machine the delivery of the detergent product into the wash liquor is maintained at a constant level during an extended period of machine operating time.
- It is a further object of the invention to provide a detergent containing sachet which is suitable for single tank reuse machines such that during consecutive washing cycles the concentration of the detergent product in the wash liquor is maintained at a constant level.
- It is a still further object of the invention that this constant level of detergent product is maintained during at least 15 consecutive washing cycles. It is another object of the invention that this detergent containing sachet can be simply prepared.
- We have now surprisingly found that a constant delivery of detergent product can be obtained if the sachet contains both detergent powder and solid detergent briquettes. In this context, briquettes are defined as solid detergent blocks which include several discretely shaped detergent particles such as tablets, cubes, etc.
- The present invention provides a sachet containing a detergent composition and adapted for use in association with a dishwashing machine wherein the detergent comprises 20-350 grams of detergent powder and one or more solid detergent briquettes, the weight of each briquette being in the range of 1-1OO grams and the total weight of the briquettes being 10-200 grams. A second aspect of the present invention concerns a process for the preparation of this sachet wherein the solid detergent briquettes are produced by compression and, thereafter, the sachet is filled with these detergent briquettes and with detergent powder. A third aspect of the invention relates to the use of the sachet in an industrial ware washing machine.
- The sachet of the invention is designed to deliver its contents in distinctly different ways: the detergent powder is released very rapidly to obtain the required detergent concentration in the first wash whereas the release of the material of the solid briquettes is delayed and/or retarded such that the drop in detergent concentration caused by the dilution effect of rinse water applied between consecutive washes is compensated for.
- The material of which the sachet is made, may be water permeable, water dispersable or water soluble material. Very practical are sachets made of water soluble material, such as polyvinyl alcohol, polyethylene oxide and methyl cellulose. For technical and economical reasons polyvinyl alcohol (PVA) is preferably used as water soluble material. Most preferably, a PVA-film is used containing in addition to PVA starch, plasticiser and water, such as the PVA-film coded LXP 910 1.5 mil supplied by Chris Craft Monosol USA.
- Both briquettes and powder generally contain detergent components usually found in detergent material suitable for use in industrial ware washing machines. These detergent components comprise a builder, an alkaline agent, a bleaching agent and one or more types of nonionic surfactant material.
- Alkaline agents which can be suitably used as constituents in the detergent composition of the invention are sodium- or potassium-hydroxide, -metasilicate and -carbonate. Preferred alkaline agents are sodium-metasilicate and -carbonate. The total level of alkaline agents is in the range of from 10% to 80% by weight, preferably from 30% to 70% by weight of the detergent composition.
- The detergent composition of the invention contains at least one type of builder material capable of reducing the level of free calcium ions in the wash liquor and preferably providing the composition with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the substrate to be cleaned. The total level of the detergency builder may be from 10% to 70% by weight, preferably from 30% to 60% by weight of the detergent composition.
Preferred builders are phosphate builders such as pyrophosphate, orthophosphate or tripolyphosphate and ion exchange builders such as crystalline (zeolite) or amorphous aluminosilicates. Optionally, organic and inorganic polymers may be present; for example, polycarboxylate polymers, such as acrylic-maleic copolymers such as SOKALAN-types of polymers and acrylic acid polymers such as Norasol LMW 45 ND (ex NorsoHaas) or Goodrite K7058 D (ex BF Goodrich) may be present. Other organic detergency builders which may be effectively used in the detergent composition of the present invention are citrates, nitrilotriacetates, phytates, polyphosphonates, oxydisuccinates, oxydiacetates, carboxymethyloxy succinates, tetracarboxylates and oxidised heteropolymeric polysaccharides. Other preferred builder systems are precipitant builders such as those containing calcite and carbonate as described in EP-A-267 042. - The detergent composition of the invention may, further, contain 1-5% by weight of an active chlorine bleach such as sodium dichloro-isocyanurate, or, alternatively, 5-20% by weight of an oxygen bleach such as a peroxy acid compound. Preferably, an active chlorine bleach component is applied.
- It is furthermore desirable to use an anti-foam agent such as a low-foaming nonionic surfactant in the wash liquor and such agents may indeed be incorporated in the detergent composition of the invention. Amounts of 0-5% by weight proved to be suitable.
- The detergent composition of the invention may further comprise suitable minor ingredients, such as bleach stabilizers, enzymes, etc. Additional components particularly suitable for the briquettes may be compaction aids, for instance calcium stearate, hydrophobic silica or talc powder.
- Usually, the amount of detergent powder in a sachet according to the present invention is in the range 25-200 grams. Preferably, 30-80 grams of detergent powder is applied. Furthermore, the total weight of the detergent briquettes in such a sachet is also usually in the range 25-200 grams. Preferably, 30-95 grams of detergent briquettes is applied. So, the weight of the total detergent composition in the sachet is, preferably, in the range 60-175 grams.
- To obtain a good concentration profile of the detergent product in the wash liquor, the weight of each solid detergent briquette is preferred to be in the range 4-10 grams. The best results with regard to constantness of product delivery are obtained if a solubility modifier is incorporated in the solid detergent briquettes. The effect of this solubility modifier is that the delivery of the solid detergent briquettes into the wash liquor is retarded.
- Good results are obtained if, from 0.1-10% by weight, preferably from 1-3% by weight, of the solubility modifier as calculated on the total mass of the detergent is incorporated in the solid detergent briquettes. The solubility modifier is preferably selected from the group consisting of metal salts of fatty acids containing 12-24 C-atoms, more preferably 18-22 C-atoms. More preferably,the solubility modifier is selected from earth alkali metal stearates and behenates, such as magnesium stearate, calcium stearate or calcium behenate. The most effective solubility modifier appeared to be a combination of an earth alkali metal stearate and an earth alkali metal behenate.
The solid detergent briquettes may be prepared by compression or by hydration followed by solidification. They are preferably prepared by compression of detergent powder, in a BEPEX briquetting machine using a pressure ranging from 50 to 200 kN. - The sachet according to the present invention is particularly suitable to be applied in an industrial single tank reuse ware washing machine.
It was found that when using this sachet the product concentration in the wash liquor can be kept more or less constant during at least 15 consecutive washing cycles. - When used in a washing machine, the sachet is preferably placed in the dispenser according to the British application 91 07083.9. This dispenser has a distinctive size and shape and is equipped with a sink reservoir and view holes so that it can be refilled in time with a new sachet according to the present invention. Another type of dispensing device which can be effectively used, is a floating ring with a nett or grid onto which the sachet is placed. This type of dispenser is particularly effective in washing machines which do not have a protective bottom plate between the wash compartment and the wash tank.
By using these dispensers, no dosing equipment is required, optimal use of the detergent material can be achieved and the risk of skin contact when handling the product is minimised. - The invention is further illustrated by the following non-limiting examples, in which parts and percentages are by weight unless otherwise stated and by the following Figures of which:
- Fig. 1 shows the effect of the briquette size on the delivery profile obtained with a water soluble sachet containing detergent powder and briquettes, by depicting the concentration of the product in the wash liquor (in grams/liter) during 20 consecutive washes, for 2 different sizes of the briquettes applied.
- Fig. 2 shows the effect of the amount of solubility modifier incorporated in the briquettes on the delivery profile obtained with a water soluble sachet containing powder and tablets by depicting the concentration of the product in the wash liquor (in grams/liter) during 30 consecutive washes, for 4 different amounts of solubility modifier. In this figure, also a delivery profile is shown when applying sachets which only contain detergent powder.
- Fig. 3 shows a delivery profile when applying briquettes in which 1% calcium behenate and 2% magnesium stearate are incorporated as solubility modifier.
- In the examples the following abbreviations are used:
- STP
- : sodium tripolyphosphate
- SMS Oaq
- : anhydrous sodium metasilicate
- Plurafac LF 403
- : nonionic surfactant, BASF brandname
- Na.DCCA.2H2O
- : sodium dichloro-isocyanurate dihydrate
- Triton DF 12
- : nonionic surfactant, Rohm and Haas brandname
- Norasol LMW 45 ND
- : poly-acrylate, MW 4000, Norsohaas brandname
- A detergent powder and 2 types of detergent briquettes were prepared, having the following compositions:
powder (wt%) briquette I (wt%) briquette II (wt%) STP 53.0 53.0 53.0 Soda 17.8 15.8 15.8 SMS Oaq 25.0 25.0 25.0 Plurafac LF 403 1.7 1.7 1.7 Na.DCCA.2H2O 2.5 2.5 2.5 Magnesium stearate - 2.0 - Calcium stearate - - 4.0 - In briquette I magnesium stearate is incorporated as solubility modifier, whereas calcium stearate is the solubility modifier in briquette II. Two water soluble sachets consisting of PVA material, were filled with 86 grams of briquette II and 71 grams of detergent powder, the only difference between the contents of the two sachets being that the individual briquettes in one sachet have a weight of 4.2 grams whereas in the other sachet their weight is 8.3 gram.
- The water-soluble sachets were applied in a single tank reuse automatic ware washing machine (Electrolux type D 48-740) and the delivery profiles were obtained by sampling the wash liquor and subsequently carrying out alkalinity titrations of these samples. For the washing cycles 15°GH water was used.
- In figure 1 these delivery profiles are shown; the line with triangles is the profile obtained with the sachets containing the 4.2 grams briquettes, whereas the line with circles is the profile obtained with the 8.3 gram briquettes. It can be seen from figure 1 that during the first 15 washing cycles a better delivery profile of the detergent containing sachet was obtained when using 8.3 gram briquettes than with 4.2 gram briquettes.
- 4 types of detergent tablets as well as detergent powder were prepared, having the following compositions:
Number Tablet (%wt) Powder (%wt) 1 2 3 4 5 STP 42.25 42.25 42.25 42.25 42.25 NaOH prills 41.75 41.05 40.25 39.75 42.25 SMS Oaq 5.00 5.00 5.00 5.00 5.00 Triton DF 12 2.00 2.00 2.00 2.00 2.00 Na.DCCA.2H2O 3.50 3.50 3.50 3.50 3.50 Calcium stearate 0.50 1.20 2.00 2.50 0.00 Acrysol LMW 45 ND 5.00 5.00 5.00 5.00 5.00 - These formulations differ mainly as far as their concentration of solubility modifier (i.e. calcium stearate) is concerned.
- 5 different detergent containing water soluble sachets were obtained by filling them with the above detergent compositions. Each one of these sachet was specifically filled with one of the shown briquette or powder materials.
The total weight of the detergent containing sachets was 150 grams, whereas the weight of each separate tablets was 4 grams. These water-soluble sachets which consisted of PVA material were applied in a single tank reuse automatic ware washing machine (Electrolux type D48-740) and the delivery profiles were obtained by applying the method of example 1. - In figure 2 these delivery profiles are shown; each of the profiles is given a number which corresponds to the number of the composition shown in the above table. It can be derived from this table and figure 2 that the solubility of the detergent briquettes was more retarded if more calcium-stearate was incorporated in these tablets.
-
- A water soluble sachet consisting of PVA material, was filled with 86 gram of these briquettes and 73 gram of this detergent powder. The sachet was applied in a single tank reuse automatic ware washing machine (Electrolux type D48-740) and the delivery profile was obtained by applying the method of example 1. In figure 3 this profile is shown. It can be seen that a reasonably constant concentration of the detergent product in the wash liquor was obtained during more than 10 washes.
- Three different types of water soluble sachet were produced. These sachets which respectively consisted of the following PVA-containing materials:
- a) Monosol E2060 ex Chris Craft Monosol USA;
- b) LXP 910 1.5 mil ex Chris Craft Monosol USA;
- c) LXP 917 2.0 mil ex Chris Craft Monosol USA;
- It can be seen that the LXP 910 1.5 mil film was found to be the most suitable PVA-containing material for the sachet of the present invention.
Subsequently, the sachets were packed in polyethene outer-sachets and stored for 6 weeks at -18°C, ambient temperature and 37°C. The following results with regard to the condition of the PVA-containing type of material of which the sachets were made, were obtained:
-18°C | ambient | 37°C | |
Sachet LXP 910 1.5 mil film | good | good | good |
Sachet E2060 film | brittle | good | brittle |
Sachet LXP 917 2.0 mil film | moderate | moderate | brittle |
Claims (11)
- A sachet containing a detergent composition and adapted for use in association with a dishwashing machine wherein said detergent composition comprises 20-350 grams of both detergent powder and one or more solid detergent briquettes, the weight of each briquette being in the range 1-100 grams and the total weight of the briquettes being 10-200 grams.
- The sachet according to claim 1, wherein the weight of each detergent briquette is in the range 4-10 grams.
- The sachet according to claims 1 or 2, wherein the total weight of the detergent powder is 30-80 grams, and the total weight of the detergent briquettes is 30-95 grams.
- The sachet according to any of claims 1-3, wherein from 0.1 to 10% by weight of a solubility modifier as calculated on the total mass of the detergent is incorporated in the material of the briquettes.
- The sachet according to claim 4, wherein from 1 to 3% by weight of the solubility modifier as calculated on the total mass of the detergent is incorporated in the material of the briquettes.
- The sachet according to claim 4 or 5, wherein the solubility modifier is selected from the group, consisting of metal salts of fatty acids containing 12-24 C-atoms.
- The sachet according to claim 6, wherein the solubility modifier is a combination of an earth alkali metal-stearate and an earth alkali metal behenate.
- The sachet according to any of claims 1-7, wherein the material of which the sachet is made contains polyvinyl alcohol, starch, plasticizer and water.
- Process for the preparation of the sachet according to any of claim 1-8, wherein the solid detergent briquettes are produced by compression and thereafter the sachet is filled with these detergent briquettes and detergent powder.
- Use of the sachet according to any of claim 1-8 in an industrial ware washing machine.
- Use of the sachet according to any of claims 1-8 in an industrial single tank reuse ware washing machine.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9107100 | 1991-04-04 | ||
GB919107100A GB9107100D0 (en) | 1991-04-04 | 1991-04-04 | Detergent containing article |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0507404A2 true EP0507404A2 (en) | 1992-10-07 |
EP0507404A3 EP0507404A3 (en) | 1993-01-20 |
EP0507404B1 EP0507404B1 (en) | 1996-05-15 |
Family
ID=10692653
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92200913A Expired - Lifetime EP0507404B1 (en) | 1991-04-04 | 1992-03-31 | Detergent containing article |
Country Status (9)
Country | Link |
---|---|
US (1) | US5294361A (en) |
EP (1) | EP0507404B1 (en) |
AU (1) | AU649525B2 (en) |
CA (1) | CA2064675C (en) |
DE (1) | DE69210669T2 (en) |
ES (1) | ES2087430T3 (en) |
FI (1) | FI106869B (en) |
GB (1) | GB9107100D0 (en) |
NZ (1) | NZ242178A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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US5518646A (en) * | 1993-04-01 | 1996-05-21 | Lever Industrial Company, Division Of Indopco, Inc. | Solid detergent briquettes |
WO1997001625A1 (en) * | 1995-06-27 | 1997-01-16 | Johnson Company, Ltd. | A detergent for use in an automatic dishwasher |
WO2001004258A1 (en) * | 1999-07-09 | 2001-01-18 | Henkel Kommanditgesellschaft Auf Aktien | Detergent or cleaning agent portion |
WO2001029172A1 (en) * | 1999-10-21 | 2001-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Dishwasher detergent portion |
WO2005097966A1 (en) * | 2004-04-08 | 2005-10-20 | Unilever Plc | Delivery system for an active agent |
EP1624017A1 (en) * | 2004-07-12 | 2006-02-08 | The Procter & Gamble Company | Packaged composition for the delivery of said composition into an aqueous medium |
US7083047B2 (en) | 2002-10-03 | 2006-08-01 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Polymeric film for water soluble package |
US7417019B2 (en) | 2000-07-14 | 2008-08-26 | Henkel Kommanditgesellschaft Auf Aktien | Hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent |
EP2199386A1 (en) | 1993-10-08 | 2010-06-23 | Novozymes A/S | Amylase variants |
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US5456854A (en) * | 1992-06-19 | 1995-10-10 | Amway Corporation | Dispensible powder detergent |
US6037319A (en) * | 1997-04-01 | 2000-03-14 | Dickler Chemical Laboratories, Inc. | Water-soluble packets containing liquid cleaning concentrates |
US6136776A (en) * | 1997-04-01 | 2000-10-24 | Dickler Chemical Laboratories, Inc. | Germicidal detergent packet |
DE19726141A1 (en) * | 1997-06-19 | 1999-01-28 | Daum Gmbh | Device for inserting medical instrument into neuronal part of head |
DE19935257A1 (en) * | 1999-07-27 | 2001-02-08 | Henkel Ecolab Gmbh & Co Ohg | Portioned cleaning tablets |
US20040033928A1 (en) * | 2000-10-31 | 2004-02-19 | The Procter & Gamble Company | Method of reblending detergent tablets |
US20040038849A1 (en) * | 2000-10-31 | 2004-02-26 | The Procter & Gamble Company | Reblending of detergent tablets |
US6475977B1 (en) * | 2001-03-16 | 2002-11-05 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Water soluble sachet with a dishwasher composition |
US6492312B1 (en) * | 2001-03-16 | 2002-12-10 | Unilever Home & Personal Care Usa, Division Of Conopco, Inc. | Water soluble sachet with a dishwashing enhancing particle |
ES2375224T3 (en) * | 2001-05-14 | 2012-02-27 | The Procter & Gamble Company | CLEANING PRODUCT. |
US6486109B1 (en) * | 2001-06-18 | 2002-11-26 | Colgate-Palmolive Company | Cleaning system including a liquid cleaning composition disposed in a water soluble container |
US6444632B1 (en) * | 2001-06-18 | 2002-09-03 | Colgate-Palmolive Company | Cleaning system including a liquid cleaning composition disposed in a water soluble container |
GB2385599A (en) | 2002-02-26 | 2003-08-27 | Reckitt Benckiser Nv | Packaged detergent composition |
US6924259B2 (en) * | 2002-04-17 | 2005-08-02 | National Starch And Chemical Investment Holding Corporation | Amine copolymers for textile and fabric protection |
EP1551712A1 (en) * | 2002-10-09 | 2005-07-13 | The Procter & Gamble Company | Process for making water-soluble pouches |
US6605578B1 (en) * | 2003-03-05 | 2003-08-12 | Colgate-Palmolive Co. | Automatic dishwashing cleaning system |
ATE550420T1 (en) * | 2007-12-05 | 2012-04-15 | Procter & Gamble | PACKAGING WITH A CLEANING AGENT |
EP2318499B1 (en) * | 2008-07-14 | 2013-03-06 | 3M Innovative Properties Company | Method of making a cleaning solution from hydrogel cleaning concentrate and packaged cleaning concentrate |
US10184097B2 (en) * | 2013-02-08 | 2019-01-22 | Ecolab Usa Inc. | Protective coatings for detersive agents and methods of forming and detecting the same |
US10800587B2 (en) | 2018-06-29 | 2020-10-13 | Henkel IP & Holding GmbH | Separatable agent doses |
AU2020283131A1 (en) | 2019-05-30 | 2021-12-23 | Ecolab Usa Inc. | Dispensing system for transferring chemical into a strainer basket assembly |
US11542460B2 (en) | 2021-04-14 | 2023-01-03 | Henkel Ag & Co. Kgaa | Multi-chamber detergent single dose packs with detachable and reattachable functionality and methods of using the same |
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-
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- 1992-03-31 ES ES92200913T patent/ES2087430T3/en not_active Expired - Lifetime
- 1992-03-31 EP EP92200913A patent/EP0507404B1/en not_active Expired - Lifetime
- 1992-03-31 NZ NZ242178A patent/NZ242178A/en not_active IP Right Cessation
- 1992-03-31 DE DE69210669T patent/DE69210669T2/en not_active Expired - Fee Related
- 1992-04-01 FI FI921421A patent/FI106869B/en not_active IP Right Cessation
- 1992-04-01 CA CA002064675A patent/CA2064675C/en not_active Expired - Fee Related
- 1992-04-03 US US07/862,645 patent/US5294361A/en not_active Expired - Lifetime
- 1992-04-03 AU AU14054/92A patent/AU649525B2/en not_active Ceased
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EP0314890A2 (en) * | 1987-10-02 | 1989-05-10 | Ecolab Inc. | Dispenser for an article comprising a water soluble bag containing a pelletized functional material, and methods for its use |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5518646A (en) * | 1993-04-01 | 1996-05-21 | Lever Industrial Company, Division Of Indopco, Inc. | Solid detergent briquettes |
EP2199386A1 (en) | 1993-10-08 | 2010-06-23 | Novozymes A/S | Amylase variants |
WO1997001625A1 (en) * | 1995-06-27 | 1997-01-16 | Johnson Company, Ltd. | A detergent for use in an automatic dishwasher |
WO2001004258A1 (en) * | 1999-07-09 | 2001-01-18 | Henkel Kommanditgesellschaft Auf Aktien | Detergent or cleaning agent portion |
WO2001029172A1 (en) * | 1999-10-21 | 2001-04-26 | Henkel Kommanditgesellschaft Auf Aktien | Dishwasher detergent portion |
US7417019B2 (en) | 2000-07-14 | 2008-08-26 | Henkel Kommanditgesellschaft Auf Aktien | Hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent |
US7601679B2 (en) | 2000-07-14 | 2009-10-13 | Henkel Ag & Co. Kgaa | Process for producing a hollow body with a compartment, containing a portion of a washing, cleaning or rinsing agent |
US7083047B2 (en) | 2002-10-03 | 2006-08-01 | Unilever Home & Personal Care Usa Division Of Conopco, Inc. | Polymeric film for water soluble package |
WO2005097966A1 (en) * | 2004-04-08 | 2005-10-20 | Unilever Plc | Delivery system for an active agent |
EP1624017A1 (en) * | 2004-07-12 | 2006-02-08 | The Procter & Gamble Company | Packaged composition for the delivery of said composition into an aqueous medium |
WO2006017303A1 (en) * | 2004-07-12 | 2006-02-16 | The Procter & Gamble Company | Packaged composition for the delivery of said composition into an aqueous medium |
Also Published As
Publication number | Publication date |
---|---|
CA2064675C (en) | 1998-06-30 |
FI921421A0 (en) | 1992-04-01 |
FI106869B (en) | 2001-04-30 |
DE69210669D1 (en) | 1996-06-20 |
US5294361A (en) | 1994-03-15 |
FI921421A (en) | 1992-10-05 |
EP0507404B1 (en) | 1996-05-15 |
NZ242178A (en) | 1994-02-25 |
DE69210669T2 (en) | 1996-09-26 |
AU1405492A (en) | 1992-10-08 |
ES2087430T3 (en) | 1996-07-16 |
AU649525B2 (en) | 1994-05-26 |
CA2064675A1 (en) | 1992-10-05 |
EP0507404A3 (en) | 1993-01-20 |
GB9107100D0 (en) | 1991-05-22 |
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